Cleavage of Cobalt-Alkyl Bonds of N-Dialkyleobalt (III) Complexes with Organic Oxidants Catalyzed by Mg(CIO4)2 and HCIO4

Shunichi Fukuzumi, Kunio Ishikawa, Toshio Tanaka

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Electron transfer from crs-dialkylcobalt (III) complexes, cis-[R2Co(bpy)2]C1O4 (R=Me, Et; bpy=2, 2'-bipyridine), to strong organic oxidants (2, 3-dichloro-5, 6-dicyano-p-benzoquinone, 2, 3-dieyano-p-benzoquinone, tetracyanoethylene, and 7, 7, 8, 8-tetraeyano-p-quinodimethan) in aeetonitrile results in the cleavage of a pair of the cobalt-alkyl bonds to yield the coupled products (R-R) exclusively. The cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with weaker organic oxidants such as p-benzoquinone was catalyzed significantly by Mg(C1O4)2 and HC1O4. The presence of both Mg(C1O4)2 and HC1O4 showed a much larger catalytic effect than that of Mg(C1O4)2 or HC1O4 alone. It has been studied a correlation of the logarithm of rate constants with the difference of the redox potentials between cis-[R2Co(bpy)2]+ and the oxidants in the absence and presence of Mg(C1O4)2, and presence of both Mg(C1O4)2 and HC1O4. Then, the role of Mg(C1O4)2 and HC1O4 in the cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with p-benzoquinone derivatives was found to be due to the increased electron-accepting property of the oxidants, resulting in the acceleration of electron transfer from cis-[R2Co(bpy)2]+ to the oxidants.

Original languageEnglish
Pages (from-to)62-69
Number of pages8
JournalNIPPON KAGAKU KAISHI
Volume1985
Issue number1
DOIs
Publication statusPublished - Jan 1 1985
Externally publishedYes

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Cobalt
Oxidants
Electrons
2,2'-Dipyridyl
Rate constants
Derivatives
benzoquinone

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Cleavage of Cobalt-Alkyl Bonds of N-Dialkyleobalt (III) Complexes with Organic Oxidants Catalyzed by Mg(CIO4)2 and HCIO4. / Fukuzumi, Shunichi; Ishikawa, Kunio; Tanaka, Toshio.

In: NIPPON KAGAKU KAISHI, Vol. 1985, No. 1, 01.01.1985, p. 62-69.

Research output: Contribution to journalArticle

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abstract = "Electron transfer from crs-dialkylcobalt (III) complexes, cis-[R2Co(bpy)2]C1O4 (R=Me, Et; bpy=2, 2'-bipyridine), to strong organic oxidants (2, 3-dichloro-5, 6-dicyano-p-benzoquinone, 2, 3-dieyano-p-benzoquinone, tetracyanoethylene, and 7, 7, 8, 8-tetraeyano-p-quinodimethan) in aeetonitrile results in the cleavage of a pair of the cobalt-alkyl bonds to yield the coupled products (R-R) exclusively. The cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with weaker organic oxidants such as p-benzoquinone was catalyzed significantly by Mg(C1O4)2 and HC1O4. The presence of both Mg(C1O4)2 and HC1O4 showed a much larger catalytic effect than that of Mg(C1O4)2 or HC1O4 alone. It has been studied a correlation of the logarithm of rate constants with the difference of the redox potentials between cis-[R2Co(bpy)2]+ and the oxidants in the absence and presence of Mg(C1O4)2, and presence of both Mg(C1O4)2 and HC1O4. Then, the role of Mg(C1O4)2 and HC1O4 in the cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with p-benzoquinone derivatives was found to be due to the increased electron-accepting property of the oxidants, resulting in the acceleration of electron transfer from cis-[R2Co(bpy)2]+ to the oxidants.",
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AB - Electron transfer from crs-dialkylcobalt (III) complexes, cis-[R2Co(bpy)2]C1O4 (R=Me, Et; bpy=2, 2'-bipyridine), to strong organic oxidants (2, 3-dichloro-5, 6-dicyano-p-benzoquinone, 2, 3-dieyano-p-benzoquinone, tetracyanoethylene, and 7, 7, 8, 8-tetraeyano-p-quinodimethan) in aeetonitrile results in the cleavage of a pair of the cobalt-alkyl bonds to yield the coupled products (R-R) exclusively. The cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with weaker organic oxidants such as p-benzoquinone was catalyzed significantly by Mg(C1O4)2 and HC1O4. The presence of both Mg(C1O4)2 and HC1O4 showed a much larger catalytic effect than that of Mg(C1O4)2 or HC1O4 alone. It has been studied a correlation of the logarithm of rate constants with the difference of the redox potentials between cis-[R2Co(bpy)2]+ and the oxidants in the absence and presence of Mg(C1O4)2, and presence of both Mg(C1O4)2 and HC1O4. Then, the role of Mg(C1O4)2 and HC1O4 in the cleavage of the cobalt-alkyl bonds of cis-[R2Co(bpy)2]+ with p-benzoquinone derivatives was found to be due to the increased electron-accepting property of the oxidants, resulting in the acceleration of electron transfer from cis-[R2Co(bpy)2]+ to the oxidants.

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